CN101899306B - Nanoparticles with core-shell structure and near-infrared fluorescence and preparation method thereof - Google Patents
Nanoparticles with core-shell structure and near-infrared fluorescence and preparation method thereof Download PDFInfo
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- CN101899306B CN101899306B CN 200910085030 CN200910085030A CN101899306B CN 101899306 B CN101899306 B CN 101899306B CN 200910085030 CN200910085030 CN 200910085030 CN 200910085030 A CN200910085030 A CN 200910085030A CN 101899306 B CN101899306 B CN 101899306B
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Abstract
The invention belongs to the fluorescent material field and relates to nanoparticles with the core-shell structure and near-infrared fluorescence and a preparation method thereof. The preparation method comprises the following steps: adopting the coordination precipitation method to prepare rare earth inorganic salt nanometer core nanoparticles doped with near-infrared luminous rare earth ions; then not separating, and adopting the one pot method to directly grow an inorganic salt shell layer without the doped rare earth ions on the outer surface of the rare earth inorganic salt nanometer core nanoparticles to obtain the nanoparticles with the core-shell structure and near-infrared fluorescence, wherein organic ligands are covered on the outer surface of the rare earth inorganic salt nanoparticles doped with rare earth ions in the core-shell structure. The nanoparticles of the invention can be used as the active material in the fields such as the polymer waveguide amplifier material and the biological fluorescence labeled substance.
Description
Technical field
The invention belongs to the fluorescent material field, particularly have the nanoparticle and preparation method thereof of the nucleocapsid structure of near-infrared fluorescence.
Background technology
Rare earth ion doped fluorescent nano particles is widely used, and wherein near-infrared luminous nanoparticle receives much attention due to fields such as can being applied to image intensifer, biomarker, laser.In recent years, along with the development of integrated optics, the research of flat optical waveguide amplifier becomes focus, and research is matrix mainly with inorganic multicomponent glass at present, mixes rare earth ion as active media.With respect to the inorganic planar optical waveguide amplifier, the organic optical waveguide amplifier technical process take polymkeric substance as matrix is simple, there is no the step of pyroprocessing, and cost is low, is easy to other device integrated.Along with going deep into of research, it is found that in rear-earth-doped polymer materials, rare earth ion near-infrared luminous is vulnerable to the impact of surrounding environment and quencher, for example with ErCl
3Directly be incorporated in polymethylmethacrylate (PMMA), even be difficult to observe fluorescence.And with organic group, that the effect that rare earth ion protects is also undesirable, because the c h bond multiple-frequency vibration in organic group is positioned at the 1480nm left and right, also be easy to the fluorescence of the 1550nm of quencher erbium.Use well-designed cage compound that erbium ion is wrapped up, away from hydroxyl and hydrocarbon key, for example vanVeggel has reported use polydentate ligand parcel erbium ion in the literature, improved fluorescence lifetime, but still only has 0.5 microsecond (Slooff, L.H., et al., Optical properties of erbium-doped organicpolydentate cage complexes.Journal of Applied Physics, 1998.83 (1): p.497-503), far do not reach the requirement of device.Another method is used fluoropolymer or fluorine-containing part exactly, in (per) fluoropolymer the life-span of erbium ion very long, can reach Millisecond, but dispersed very poor, be difficult to reach the requirement of device fabrication.Compare with aforesaid method, rare earth ion doped inorganic nano-particle has obvious advantage, be in due to rare earth ion in the lattice of nanoparticle, isolate with the quencher group, and the phonon vibration energy level of inorganic lattice is low, greatly reduced the probability of rare earth ion multi-phonon nonradiative transition, thus the fluorescence lifetime that has greatly extended rare earth ion.Use the synthetic nanoparticle of hydrothermal method or solution method still to have good dispersiveness when having the good fluorescence performance in organic solvent, can be used as the active material of polymer waveguide amplifier device.
The quencher group of rare earth ion doped nanoparticle surface and lattice imperfection are still very large for the impact of luminescent properties, can grow the inorganic shell of one deck with the quencher group of insulation surfaces in nanoparticle surface in order further to improve luminous efficiency, but SiO commonly used
2And TiO
2Shell is not thorough to the organic group isolation of most finishing, the more important thing is, due to SiO
2And TiO
2Different with the crystal formation of nanometer nuclear particle, can't eliminate the lattice imperfection position on nanometer nuclear particle surface.Therefore the present invention has designed in the scheme of nanometer nuclear particle surface growth with mutually isomorphous shell, so not only can eliminate surface imperfection but also quencher group that can insulation surfaces, thereby reaches the purpose of raising fluorescence property.The method that the present invention uses is the coordination precipitation method, and is good for the synthesis of the versatility of nanoparticle, and all carries out in same solution synthesizing with the growth of shell of nuclear particle, saved the separating step of intermediate product, easy and simple to handle, is convenient to amplify and produces.
Summary of the invention
The nanoparticle that the purpose of this invention is to provide the nucleocapsid structure with near-infrared fluorescence.
A further object of the present invention is to provide a kind of preparation method of nanoparticle of the nucleocapsid structure with near-infrared fluorescence.
The present invention adopts the standby near-infrared luminous rare earth ion doped inorganic salt of rare earth nanometer nuclear particle of coordination precipitation legal system, does not then separate, and one kettle way is directly at the undope inorganic salt shell of rare earth ion of inorganic salt of rare earth nanometer nuclear particle outside surface growth one deck.
Described nanoparticle with nucleocapsid structure of near-infrared fluorescence is that the outside surface at the rare earth ion doped inorganic salt of rare earth nanoparticle of nucleocapsid structure is coated with organic ligand, wherein:
The core of described inorganic salt of rare earth nanoparticle be by as cationic rare earth ion with as the F of negatively charged ion
-, PO
4 3-, VO
4 3-Deng in a kind of formation; Wherein, form as the rare earth ion of cationic rare earth ion by near-infrared luminous rare earth ion and inertia, the molar ratio of near-infrared luminous rare earth ion and the rare earth ion of inertia is 0.01～0.2;
Described shell is by as the rare earth ion of cationic inertia and F as negatively charged ion
-, PO
4 3--, VO
4 3-Deng in a kind of inorganic salt of rare earth of formation;
The molar ratio of the near-infrared luminous rare earth ion in the rare earth ion of the inertia in described shell and nuclear particle and the rare earth ion sum of inertia is 1～3.
Described near-infrared luminous rare earth ion is selected from Er
3+(erbium ion), Yb
3+(ytterbium ion), Nd
3+(neodymium ion), Pr
3+(praseodymium ion), Tm
3+(thulium ion), Sm
3+(samarium ion), Ho
3+At least a in the group that (holmium ion) etc. forms.
The rare earth ion of described inertia is La
3+(lanthanum ion), Lu
3+(lutetium ion), Y
3+A kind of in the rare earth ion of inertia such as (ruthenium ions).
Described organic ligand is selected from a kind of in tributyl phosphate, oleic acid, sodium oleate, citric acid, ammonium citrate.
The schematic diagram of the nanoparticle of the nucleocapsid structure with near-infrared fluorescence of the present invention as shown in Figure 1, it is that outside surface at the particle of almost spherical is coated with organic ligand, wherein the diameter of nuclear particle is 4～8nm, the thickness of shell is 2～8nm.
The preparation method of the nanoparticle of the nucleocapsid structure with near-infrared fluorescence of the present invention comprises the following steps:
(1) core of synthesizing rare-earth inorganic salt nano particles at first
Rare earths salt, organic ligand and solvent are evenly formed mixed solution, and wherein: the concentration of the rare-earth salts in mixed solution is 0.01～0.1M, and the concentration of organic ligand is 0.01～1M, and the concentration of alcohol is 0.1～2M; Under protection of inert gas, after the heating mixed solution is 20～200 ℃ to temperature of reaction, add precipitant solution, wherein the molar ratio of the solute in precipitant solution and the rare earth ion in rare earths salt is 1～16, reaction times is 30min～3h, obtains containing the solution of the core of inorganic salt of rare earth nanoparticle;
(2) synthetic nanoparticle with nucleocapsid structure of near-infrared fluorescence
add the rare earths salt that forms shell in the solution of the core that contains the inorganic salt of rare earth nanoparticle that obtains to step (1), organic ligand and solvent form mixed solution, add again precipitant solution, wherein: in the rare earths salt that adds in contained rare-earth salts and step (1) in mixed solution the molar ratio of contained rare-earth salts be 1～3, in the organic ligand that adds and step (1), the molar ratio of organic ligand is 1～3, in the alcohol that adds and step (1), the molar ratio of alcohol is 1～3, in the precipitant solution that adds in contained precipitation agent and step (1) in mixed solution the molar ratio of contained precipitation agent be 1～3, be that 20～200 ℃ of lower reaction times are 30min～3h in temperature of reaction, namely get the solution of the nanoparticle crude product that contains the nucleocapsid structure with near-infrared fluorescence,
The organic ligand that adds in above-mentioned steps (2) and solvent are that selection is same with organic ligand and solvent phase that step (1) adds; Which kind of organic ligand what be that step (1) adds is, just adds which kind of organic ligand in step (2), and the organic ligand that adds as step (1) is tributyl phosphate, just adds tributyl phosphate in step (2); The solvent that adds in step (1) is oleic acid, just adds oleic acid in step (2).
(3) product separation
Add a kind of in methyl alcohol, ethanol or acetone in the solution of the nanoparticle crude product that contains the nucleocapsid structure with near-infrared fluorescence that obtains to step (2), make the nanoparticle crude product precipitation of the nucleocapsid structure with near-infrared fluorescence, supernatant liquor is removed in centrifugation; The precipitation that obtains is dispersed in normal hexane, toluene or water, revolves to steam and remove normal hexane, toluene or water, namely get the nanoparticle of the nucleocapsid structure with near-infrared fluorescence.
The volume of the described methyl alcohol that adds, ethanol or acetone is 1～3 times of liquor capacity that contains the nanoparticle crude product of the nucleocapsid structure with near-infrared fluorescence.
Rare earths salt described in step (1) is formulated by a kind of solvent and the solute that are selected from water, tributyl phosphate, methyl alcohol, ethanol etc.; Wherein, described solute is selected from as the cationic rare earth ion that is comprised of the rare earth ion of near-infrared luminous rare earth ion and inertia and Cl as negatively charged ion
-, NO
3 -, CH
3COO
-, CF
3COO
-Deng in a kind of group that forms at least a composition, wherein the molar ratio of the rare earth ion of near-infrared luminous rare earth ion and inertia is 0.01～0.2.
Near-infrared luminous rare earth ion described in step (1) is selected from Er
3+(erbium ion), Yb
3+(ytterbium ion), Nd
3+(neodymium ion), Pr
3+(praseodymium ion), Tm
3+(thulium ion), Sm
3+(samarium ion), Ho
3+At least a in the group that (holmium ion) etc. forms.
Rare earths salt described in step (2) is formulated by a kind of solvent and the solute that are selected from water, tributyl phosphate, methyl alcohol, ethanol etc.; Wherein, described solute is selected from as the rare earth ion of cationic inertia and Cl as negatively charged ion
-, NO
3 -, CH
3COO
-, CF
3COO
-Deng in a kind of group that forms at least a composition.
The rare earth ion of described inertia is La
3+(lanthanum ion), Lu
3+(lutetium ion), Y
3+A kind of in the rare earth ion of inertia such as (ruthenium ions).
Described solvent is selected from least a in the group that water, tributyl phosphate, oleic acid, phenyl ether, trioctylamine, ethanol, methyl alcohol etc. form.
The solvent of described precipitant solution is selected from a kind of in water, tributyl phosphate, two hexyl ethers etc., and solute is selected from a kind of in anhydrous phosphoric acid, Sodium Fluoride, Neutral ammonium fluoride, vanadic acid sodium etc.
Described organic ligand is selected from a kind of in tributyl phosphate, oleic acid, sodium oleate, citric acid, ammonium citrate etc.
Described rare gas element is a kind of in nitrogen, helium etc.
The form almost spherical of the nanoparticle of the nucleocapsid structure with near-infrared fluorescence of the present invention's preparation, even particle size, it has good dispersiveness and fluorescence property.Preparation method of the present invention is easy and simple to handle, is easy to the nanoparticle that the nucleocapsid structure with near-infrared fluorescence is produced in extensive preparation.Nanoparticle with nucleocapsid structure of near-infrared fluorescence of the present invention can be used as active substance and is used for the fields such as polymer waveguide amplifier material and fluorescent biological labels matter.
Description of drawings
Fig. 1. the structural representation of the product of the embodiment of the present invention 1.
Fig. 2. the electromicroscopic photograph of the product of the embodiment of the present invention 1.
Fig. 3. the near-infrared fluorescent spectrogram of the product of the embodiment of the present invention 1.
Embodiment
Below in conjunction with embodiment and accompanying drawing, technical scheme of the present invention is further described, but these embodiment do not consist of the restriction to content of the present invention.
Embodiment 1
Er, Yb:LaPO
4/ LaPO
4Synthesizing of nucleocapsid structure near-infrared light-emitting material
(1) at first synthetic Er, Yb:LaPO
4/ LaPO
4The core of nanoparticle
The tributyl phosphate solution of 10mL rare earth chloride (is wherein contained 0.375mmol LaCl
3, 0.1mmol YbCl
3With 0.025mmol ErCl
3), 5.5ml trioctylamine (C
8H
17)
3N and 35ml phenyl ether mix the formation mixed solution, and under vacuum, 50～80 ℃ of underpressure distillation are 2 hours.Under nitrogen protection, after heating mixed solution to 200 ℃, add two hexyl ether solution 3.5ml of the anhydrous phosphoric acid of 2M, reacted 3 hours, obtain containing Er, Yb:LaPO
4/ LaP
OThe solution of the core of 4 nanoparticles;
(2) synthetic Er with nucleocapsid structure of near-infrared fluorescence, Yb:LaPO
4/ LaPO
4Nanoparticle
Contain Er, Yb:LaPO to what step (1) obtained
4/ LaPO
4Add the tributyl phosphate solution of 30mL Lanthanum trichloride (wherein to contain 1.5mmol LaCl in the solution of the core of nanoparticle
3), 10.5ml trioctylamine (C
8H
17)
3N and 45ml phenyl ether form mixed solution, then add two hexyl ether solution 10.5ml of the anhydrous phosphoric acid of 2M, react 3 hours, namely get and contain the Er with near-infrared fluorescence, Yb:LaPO
4/ LaPO
4The solution of core-shell structure nanometer particle crude product;
(3) product separation
Adding in the solution of the nanoparticle crude product that contains the nucleocapsid structure with near-infrared fluorescence that obtains to step (2) is the methyl alcohol of 3 times of liquor capacities that contains the nanoparticle crude product of the nucleocapsid structure with near-infrared fluorescence, make the nanoparticle crude product precipitation of the nucleocapsid structure with near-infrared fluorescence, supernatant liquor is removed in centrifugation; The precipitation that obtains is dispersed in toluene, and 40 ℃ revolve to steam and remove toluene and namely get the Er with near-infrared fluorescence that outside surface is coated with the almost spherical of tributyl phosphate, Yb:LaPO
4/ LaPO
4Core-shell structure nanometer particle.The diameter of described nuclear particle is 4nm, and the thickness of shell is 2nm.
The structural representation of product is seen Fig. 1, and electromicroscopic photograph is seen Fig. 2, and near-infrared fluorescent spectrum is seen Fig. 3, and nucleocapsid structure obviously strengthens the fluorescence intensity of nanoparticle as seen from Figure 3.
Embodiment 2
Nd:LuF
3/ LuF
3Synthesizing of nucleocapsid structure near-infrared light-emitting material
(1) at first synthetic Nd:LuF
3/ LuF
3The core of nanoparticle
The aqueous solution of the rare earth chloride of 1mL 1M (is wherein contained 0.05mmol NdCl
3And 0.95mmolLuCl
3), 1ml oleic acid, 1g sodium oleate and 20ml ethanol, 20mL water mixes the formation mixed solution, under argon shield, after the heating mixed solution is 75 ℃ to temperature of reaction, adds the aqueous solution of the NaF of 3mL 1M, reacts after 30 minutes, obtains containing Nd:LuF
3/ LuF
3The solution of the core of nanoparticle;
(2) synthetic Nd:LuF with nucleocapsid structure of near-infrared fluorescence
3/ LuF
3Nanoparticle
Contain Nd:LuF to what step (1) obtained
3/ LuF
3The LuCl that adds the 1mL 1M that forms shell in the solution of the core of nanoparticle
3The aqueous solution, 1ml oleic acid, 1g sodium oleate and 20ml ethanol, 20mL water form mixed solution; the aqueous solution that adds again the NaF of 3mL 1M; under the protection of Ar gas, be to react 3 hours under 75 ℃ in temperature of reaction, namely get the Nd:LuF that contains the nucleocapsid structure with near-infrared fluorescence
3/ LuF
3The solution of nanoparticle crude product;
(3) product separation
The Nd:LuF that contains the nucleocapsid structure with near-infrared fluorescence that obtains to step (2)
3/ LuF
3Add in the solution of nanoparticle crude product is the Nd:LuF that contains the nucleocapsid structure with near-infrared fluorescence
3/ LuF
3The ethanol that the liquor capacity of nanoparticle crude product is 1 times makes the Nd:LuF of the nucleocapsid structure with near-infrared fluorescence
3/ LuF
3Nanoparticle crude product precipitation, supernatant liquor is removed in centrifugation; The precipitation that obtains is dispersed in normal hexane, and last 40 ℃ revolve to steam and remove normal hexane, and 40 ℃ of lower vacuum-dryings are spent the night, and namely get the Nd:LuF with near-infrared fluorescence that outside surface is coated with the almost spherical of oleic acid
3/ LuF
3Core-shell structure nanometer particle.The diameter of described nuclear particle is 8nm, and the thickness of shell is 1nm.
Embodiment 3
Tm:LaF
3/ LaF
3Synthesizing of nucleocapsid structure near-infrared light-emitting material
(1) at first synthetic Tm:LaF
3/ LaF
3The core of nanoparticle
The aqueous solution of the rare earth chloride of 1mL 1M (is wherein contained 0.01mmol TmCl
3And 0.99mmolLaCl
3), 20ml oleic acid, 20g sodium oleate and 20ml ethanol, 20mL water mixes the formation mixed solution, under nitrogen protection, after the heating mixed solution is 80 ℃ to temperature of reaction, adds the NaF solution of 16mL 1M, reacts after 1 hour, obtains containing Tm:LaF
3/ LaF
3The solution of the core of nanoparticle;
(2) synthetic Tm:LaF with nucleocapsid structure of near-infrared fluorescence
3/ LaF
3Nanoparticle
Contain Tm:LaF to what step (1) obtained
3/ LaF
3The LaCl that adds the 3mL 1M that forms shell in the solution of the core of nanoparticle
3The aqueous solution, 60ml oleic acid, 60g sodium oleate and 60ml ethanol, 60mL water form mixed solution; the aqueous solution that adds again the NaF of 48mL 1M; under nitrogen protection, be to react 3 hours under 80 ℃ in temperature of reaction, namely get the Tm:LaF that contains the nucleocapsid structure with near-infrared fluorescence
3/ LaF
3The solution of nanoparticle crude product;
(3) product separation
The Tm:LaF that contains the nucleocapsid structure with near-infrared fluorescence that obtains to step (2)
3/ LaF
3Add in the solution of nanoparticle crude product is the Tm:LaF that contains the nucleocapsid structure with near-infrared fluorescence
3/ LaF
3The acetone that the liquor capacity of nanoparticle crude product is 2 times makes the Tm:LaF of the nucleocapsid structure with near-infrared fluorescence
3/ LaF
3Nanoparticle crude product precipitation, supernatant liquor is removed in centrifugation; The precipitation that obtains is dispersed in normal hexane, and last 40 ℃ revolve to steam and remove normal hexane, and 40 ℃ of lower vacuum-dryings are spent the night, and namely get the Nd:LuF with near-infrared fluorescence that outside surface is coated with the almost spherical of oleic acid
3/ LuF
3Core-shell structure nanometer particle.The diameter of described nuclear particle is 8nm, and the thickness of shell is 8nm.
Embodiment 4
Pr:LaF
3/ LaF
3Synthesizing of nucleocapsid structure near-infrared light-emitting material
(1) at first synthetic Pr:LaF
3/ LaF
3The core of nanoparticle
The aqueous solution of the lanthanon acetate of 10ml 0.5M (is wherein contained 0.1mmol Pr (CH
3CH
2COO)
3With 4.9mmol La (CH
3CH
2COO)
3), the aqueous solution of the ammonium citrate of 10ml 0.5M and the deionized water of 30ml mix the formation mixed solution, under nitrogen protection, after the heating mixed solution is 75 ℃ to temperature of reaction, adds the NH of the 0.5M of 30ml
4The aqueous solution of F, reaction 30min obtains containing Pr:LaF
3/ LaF
3The solution of the core of nanoparticle;
(2) synthetic Pr:LaF with nucleocapsid structure of near-infrared fluorescence
3/ LaF
3Nanoparticle
Contain Pr:LaF to what step (1) obtained
3/ LaF
3La (the CH that adds 10ml0.5M in the solution of the core of nanoparticle
3CH
2COO)
3The aqueous solution of ammonium citrate of the aqueous solution, 10ml 0.5M and the deionized water of 30ml mix the formation mixed solution, then add the NH of the 0.5M of 30ml
4The aqueous solution of F is to react 3 hours under 75 ℃ in temperature of reaction, namely gets the Pr:LaF that contains the nucleocapsid structure with near-infrared fluorescence
3/ LaF
3The solution of nanoparticle crude product;
(3) product separation
The Pr:LaF that contains the nucleocapsid structure with near-infrared fluorescence that obtains to step (2)
3/ LaF
3Add in the solution of nanoparticle crude product is the Pr:LaF that contains the nucleocapsid structure with near-infrared fluorescence
3/ LaF
3The methyl alcohol that the liquor capacity of nanoparticle crude product is 3 times makes the Pr:LaF of the nucleocapsid structure with near-infrared fluorescence
3/ LaF
3Nanoparticle crude product precipitation, supernatant liquor is removed in centrifugation; The precipitation that obtains is dispersed in water, revolves and steam except anhydrating, namely get the Pr:LaF that outside surface is coated with the nucleocapsid structure with near-infrared fluorescence of ammonium citrate
3/ LaF
3Nanoparticle.The diameter of described nuclear particle is 8nm, and the thickness of shell is 2nm.
Embodiment 5
Ho:LaVO
4/ LaVO
4Synthesizing of nucleocapsid structure near-infrared light-emitting material
(1) at first synthetic Ho:LaVO
4/ LaVO
4The core of nanoparticle
The aqueous solution of the rare earth nitrate of 5ml 1M (is wherein contained 0.5mmol Ho (NO
3)
3And 4.5mmolLa (NO
3)
3), the aqueous solution of the ammonium citrate of 10ml 0.5M and the deionized water of 500ml mix the formation mixed solution, under protection of inert gas, after the heating mixed solution is 70 ℃ to temperature of reaction, adds the NaVO of the 0.5M of 30ml
4The aqueous solution, the reaction 30min, obtain containing Ho:LaVO
4/ LaVO
4The solution of the core of nanoparticle;
(2) synthetic Ho:LaVO with nucleocapsid structure of near-infrared fluorescence
4/ LaVO
4Nanoparticle
Contain Ho:LaVO to what step (1) obtained
4/ LaVO
4La (the NO that adds 10ml 1M in the solution of the core of nanoparticle
3)
3The aqueous solution of ammonium citrate of the aqueous solution, 10mL 1M and the deionized water of 50ml form mixed solution, then add the NaVO of the 1M of 30ml
4The aqueous solution, temperature of reaction be under 70 ℃ the reaction 3 hours, namely get the Ho:LaVO that contains the nucleocapsid structure with near-infrared fluorescence
4/ LaVO
4The solution of nanoparticle crude product;
(3) product separation
The Ho:LaVO that contains the nucleocapsid structure with near-infrared fluorescence that obtains to step (2)
4/ LaVO
4Add in the solution of nanoparticle crude product is the Ho:LaVO that contains the nucleocapsid structure with near-infrared fluorescence
4/ LaVO
4The methyl alcohol that the liquor capacity of nanoparticle crude product is 3 times makes the Ho:LaVO of the nucleocapsid structure with near-infrared fluorescence
4/ LaVO
4Nanoparticle crude product precipitation, supernatant liquor is removed in centrifugation; The precipitation that obtains is dispersed in water, revolves and steam except anhydrating, namely get the Ho:LaVO that outside surface is coated with the nucleocapsid structure with near-infrared fluorescence of ammonium citrate
4/ LaVO
4Nanoparticle.The diameter of described nuclear particle is 6nm, and the thickness of shell is 1nm.
Claims (5)
1. the preparation method of the nanoparticle of the nucleocapsid structure with near-infrared fluorescence, is characterized in that, described method comprises the following steps:
(1) core of synthesizing rare-earth inorganic salt nano particles at first
Rare earths salt, organic ligand and solvent are evenly formed mixed solution, and wherein: the concentration of the rare-earth salts in mixed solution is 0.01～0.1M, and the concentration of organic ligand is 0.01～1M; Under protection of inert gas, after the heating mixed solution is 20～200 ℃ to temperature of reaction, add precipitant solution, wherein the molar ratio of the solute in precipitant solution and the rare earth ion in rare earths salt is 1～16, reaction times is 30min～3h, obtains containing the solution of the core of inorganic salt of rare earth nanoparticle;
(2) synthetic nanoparticle with nucleocapsid structure of near-infrared fluorescence
add the rare earths salt that forms shell in the solution of the core that contains the inorganic salt of rare earth nanoparticle that obtains to step (1), organic ligand and solvent form mixed solution, add again precipitant solution, wherein: in the rare earths salt that adds in contained rare-earth salts and step (1) in mixed solution the molar ratio of contained rare-earth salts be 1～3, in the organic ligand that adds and step (1), the molar ratio of organic ligand is 1～3, in the precipitant solution that adds in contained precipitation agent and step (1) in mixed solution the molar ratio of contained precipitation agent be 1～3, be that 20～200 ℃ of lower reaction times are 30min～3h in temperature of reaction, must contain the solution of the nanoparticle crude product of the nucleocapsid structure with near-infrared fluorescence,
The organic ligand that adds in step (2) and solvent are that selection is same with organic ligand and solvent phase that step (1) adds;
(3) product separation
Add a kind of in methyl alcohol, ethanol or acetone in the solution of the nanoparticle crude product that contains the nucleocapsid structure with near-infrared fluorescence that obtains to step (2), make the nanoparticle crude product precipitation of the nucleocapsid structure with near-infrared fluorescence, supernatant liquor is removed in centrifugation; The precipitation that obtains is dispersed in normal hexane, toluene or water, revolves to steam and remove normal hexane, toluene or water, must have the nanoparticle of the nucleocapsid structure of near-infrared fluorescence;
Rare earths salt described in step (1) is formulated by a kind of solvent and the solute that are selected from water, tributyl phosphate, methyl alcohol, ethanol; Wherein, described solute is selected from as the cationic rare earth ion that is comprised of the rare earth ion of near-infrared luminous rare earth ion and inertia and Cl as negatively charged ion
-, NO
3 -, CH
3COO
-, CF
3COO
-In a kind of group that forms at least a composition, wherein the molar ratio of the rare earth ion of near-infrared luminous rare earth ion and inertia is 0.01～0.2;
Near-infrared luminous rare earth ion described in step (1) is selected from Er
3+, Yb
3+, Nd
3+, Pr
3+, Tm
3+, Sm
3+, Ho
3+At least a in the group that forms;
Rare earths salt described in step (2) is formulated by a kind of solvent and the solute that are selected from water, tributyl phosphate, methyl alcohol, ethanol; Wherein, described solute is selected from as the rare earth ion of cationic inertia and Cl as negatively charged ion
-, NO
3 -, CH
3COO
-, CF
3COO
-In a kind of group that forms at least a composition;
The rare earth ion of described inertia is La
3+, Lu
3+, Y
3+A kind of in the rare earth ion of inertia.
2. method according to claim 1 is characterized in that: the volume of the described methyl alcohol that adds, ethanol or acetone is 1～3 times of liquor capacity that contains the nanoparticle crude product of the nucleocapsid structure with near-infrared fluorescence.
3. method according to claim 1 is characterized in that: described organic ligand is selected from a kind of in tributyl phosphate, oleic acid, sodium oleate, citric acid, ammonium citrate.
4. method according to claim 1 is characterized in that: described solvent is selected from least a in the group that water, tributyl phosphate, oleic acid, phenyl ether, trioctylamine, ethanol, methyl alcohol forms.
5. method according to claim 1 is characterized in that: the solvent of described precipitant solution is selected from a kind of in water, tributyl phosphate, two hexyl ethers, and solute is selected from a kind of in anhydrous phosphoric acid, Sodium Fluoride, Neutral ammonium fluoride, vanadic acid sodium.
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| CN106190125A (en) * | 2016-07-07 | 2016-12-07 | 上海应用技术学院 | A kind of YPO4: Eu3+micron ball luminescent material and preparation method thereof |
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| WO2008012266A1 (en) * | 2006-07-28 | 2008-01-31 | Rhodia Operations | Luminophore and core-shell luminophore precursors |
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